CN105199106B - A kind of preparation method of add-on type liquid fluorosioloxane rubber - Google Patents
A kind of preparation method of add-on type liquid fluorosioloxane rubber Download PDFInfo
- Publication number
- CN105199106B CN105199106B CN201510614864.7A CN201510614864A CN105199106B CN 105199106 B CN105199106 B CN 105199106B CN 201510614864 A CN201510614864 A CN 201510614864A CN 105199106 B CN105199106 B CN 105199106B
- Authority
- CN
- China
- Prior art keywords
- rubber
- add
- parts
- type liquid
- mass fraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to a kind of preparation method of add-on type liquid fluorosioloxane rubber：It is more than 99.5% D using purity3F、ViD4, MM be raw material, be well mixed by a certain percentage, vinyl fluoride silicone oil be made；Using vinyl fluoride silicone oil as base rubber, reinforcing agent, crosslinking agent, catalyst are added, then by techniques such as kneading, grinding, tablettings, prepare liquid fluorosilicone rubber（FSR）；By the liquid silastic under prepared FSR and same process, same recipe（LSR）Performance comparison, FSR are better than LSR in aspect of performances such as insulating properties, hydrophobic performance, high temperature resistants.This method is with short production cycle, and product has good hot tear crack performance, is easy to be stripped, and a variety of processing modes such as molding, extrusion, injection pressure can be achieved, can also realize the automated production of material.
Description
Technical field
The invention belongs to new chemical materialses technical field, and in particular to a kind of preparation side of add-on type liquid fluorosioloxane rubber
Method.
Background technology
Organosilicon material has Physical Mechanical superior under superior high and low temperature resistance (- 60 DEG C~310 DEG C), high temperature
The features such as energy, resistance to ag(e)ing, self-extinguishment；And fluorocarbon material heat endurance is good (- 27 DEG C~300 DEG C), have extremely superior resistance to
Oil and solvent resistance.But with the continuous development of industrial technology, organosilicon material gradually expose its oil resistant and solvent resistant difference
Shortcoming, and the defects of lower temperature resistance difference and not easy processing be present in organic fluorine material.
Liquid fluorosilicone rubber（Liquid Fluorosilicone Rubber abbreviations FSR）Also known as fluorinated silicones.It
It is the organic-silicon-modified polymerization that whole methyl of part methyl in polydimethylsiloxanes silicon or one side are substituted by trifluoro propyl
Thing.The polymer is with silica silicon（Si-O-Si）For molecular backbone, trifluoro propyl is side chain, and it is excellent that this structure assigns material
Cryogenic property and solvent resistance, and liquid fluorosilicone rubber is fluorinated silicones of the molecular weight below 100,000, it not only has
There are the resistant of high or low temperature, oil resistant, solvent resistance of fluorine-silicon compounded rubber stock, and most importantly adding also with liquid silastic
Work superiority, this greatly shortens the process-cycle of fluorosioloxane rubber, improves the efficiency of processing, and reduces the useless of fluorosioloxane rubber
Product rate.Liquid fluorosilicone rubber is mainly used in automobile making and aircraft industry at present.In addition, can also be by liquid fluorosilicone rubber
Application further expand to consumer commodity and health care in terms of, so as to promote the development of liquid fluorosilicone rubber.New
Liquid fluoro silicone elastomerses are also applied for the plastic part of post forming, and with fuel system and the replacement combustion in harshness
Performance required for the control diaphragm to be worked in oil.F atom has larger sucting electronic effect in trifluoro propyl, plus C-F keys
Bond distance is shorter, and preferable shielding action can be formed to C-C keys, greatly improves rubber oil-resistant, solvent resistance, makes it in high temperature
（230℃）There is down the performance of the medium such as resistance to Aviation Fuel, hydraulic oil, petroleum series and chemical reagent, be it is a kind of -68 DEG C~
The good elastomer of resistance to apolar medium at 232 DEG C；The surface energy of F atom is low, and the introducing of trifluoro propyl greatly reduces poly- silicon
The surface energy of oxygen alkane, so as to assign liquid fluorosilicone rubber excellent hydrophobic performance；The electronegativity of F atom is small, and atomic nucleus is to its beam
Reduction is tied up, causes the enhancing of polarization, and the introducing of trifluoro propyl can increase bonding atomic volume, also result in polarization and make
Enhancing, both collective effects, the insulating properties of liquid fluorosilicone rubber is caused to be better than liquid silastic.
Why liquid fluorosilicone rubber has excellent cryogenic property, is the Si-O on fluorinated silicones main chain first
Key, bond distance is longer, and the steric hindrance rotated to side base is small；The usual bond angle of 145 ° of ratios of Si-O-Si bond angles oxygen atom in sp3 hydridization
（109°）It is much bigger, make easily to rotate between Si-O keys, so as to assign the compliance of molecular backbone, make it have excellent resist cold
Property；Secondly, the strands of fluorinated silicones configuration in the shape of a spiral, the pliability of strand is bigger than C-C key or Si-C keys, molecule
Interaction force between chain is weak, and these architectural features make its liquid fluorosilicone rubber soft and high resilience, when the temperature is changed,
Active force that molecule is asked changes very little, so its various performances, particularly Flexible change is little, make it have other rubber without
The cryogenic property of method analogy；Finally, the presence of trifluoro propyl substituent methyl, the rule of dimethyl silicone polymer strand can be destroyed
Whole property, reduces the crystallization temperature and crystallization degree of polymer, and then liquid fluorosilicone rubber is had low temperature more more preferable than silicon rubber
Performance.
The preparation of liquid fluorosilicone rubber has two kinds of curing modes, and one kind is condensed type, and another kind is add-on type；Two kinds of solidifications
Oligomer used in mode is different, is mainly reflected in the difference of vulcanizing group.The vulcanizing group of condensed type is hydroxyl（-OH）, and
Add-on type vulcanizing group is vinyl（-CH=CH2）.
The liquid fluorosilicone rubber of condensed type vulcanization, the synthesis of oligomer hydroxy terminated fluorosilicone oil mainly have three kinds of modes：The first
It is ring-opening polymerisation, second is degradeds of the HMW PMFS under high-pressure water vapor effect, and the third is two functional silanes
Even contracting and miscellaneous contraction take.Ring-opening polymerisation at present is using a kind of most modes.Condensed type vulcanizing agent is multifunctional group
The balanced constant of silanol or siloxanes and metal salts of organic acids, currently used amount it is more have tetraethyl orthosilicate, aniline first
Ethyl triethoxy silicane alkane, silazane oligomer are as crosslinking agent, and wherein tetraethyl orthosilicate, anilinomethyl triethoxysilane can not
Independent role must coordinate tin catalyst.In addition, the liquid fluorosilicone rubber of condensed type vulcanization can be prepared as one-component and double
Component, single-component room temperature vulcanized liquid fluorosilicone rubber rely primarily on moisture or moisture progress crosslinking curing in air, had
The cementability same with general liquid silastic and it is easy to use the characteristics of, but such liquid fluorosilicone rubber during solidification due to releasing
A certain amount of small molecule is released, the cubical contraction before and after solidifying is larger, and limit makes in some special high-temperature closed fields
With.And the double component room temperature vulcanization liquid fluorosilicone rubber advantage more maximum with one-component is inside and outside when being to solidify while carries out,
Curing rate and depth are much larger than single-component room temperature vulcanized liquid fluorosilicone rubber.
The liquid fluorosilicone rubber of add-on type vulcanization, oligomer vinyl fluoride silicone oil are mainly derived from monomer D3F anion are opened
Cyclopolymerization, by controlling the conditions such as catalyst amount, reaction time, reaction temperature, system moisture, prepare to reach and meet the requirements
Product.In add-on type vulcanized liquid fluorosioloxane rubber, vinyl fluoride silicone oil is base rubber, and hydrogeneous polymer is crosslinking agent, is coordinated
Reinforcing agent, liquid fluorosilicone rubber is prepared under catalyst, polymerization inhibitor effect.Add-on type and condensed type vulcanized liquid fluorosioloxane rubber
Compared to maximum advantage be solidify when no coupling product discharge, cubical contraction is small, can directly at high temperature it is closed solidification and
Use.Can also a variety of curing modes such as cold curing, intermediate temperature setting.
But the liquid fluorosilicone rubber production method of preceding add-on type vulcanization has following deficiency：1）Be also easy to produce polymerisation in solution,
Emulsion polymerization, it is not easy to the recovery of solution, emulsion；2）Technological process is cumbersome, equipment investment is big；3）The catalyst used is usually
Long-acting catalyst is, it is necessary to which subsequent handling removes；4）Easily occur finning in process, be unfavorable for automated production.
The content of the invention
For deficiencies of the prior art, it is an object of the invention to provide a kind of add-on type liquid fluorosioloxane rubber
Preparation method.The present invention using add-on type solidification method prepares liquid fluorosilicone rubber, the material in process non-trimming,
High accuracy, it is with short production cycle, good hot tear crack performance, it is easy to be stripped, a variety of processing sides such as molding, extrusion, injection pressure can be achieved
Formula, it can also realize the automated production of material.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of preparation method of add-on type liquid fluorosioloxane rubber, comprises the following steps：
1）The synthesis of base rubber：The synthesis of base rubber：By raw material D3F、ViD4With MM by 60~70 parts of mass fraction, 0.4~0.5
Part is mixed in three-necked flask with 0.2~0.3 part, in 50 DEG C~70 DEG C removed under reduced pressure low-boiling-point substances, and adds mass fraction as 0.2
~ 0.4 catalyst, nitrogen is filled with as gas is protected, makes reaction temperature at 60 DEG C~80 DEG C, reaction time 40min~60min,
It is base rubber that ceridust base fluorosilicon oil, which is made, and the base rubber medium vinyl content is 0.02mol%~1mol%, and trifluoro propyl content is
The mol% of 20 mol%~50；Described catalyst is alkali glue；
2）The reinforcement of base rubber：By mass fraction be 100 parts base rubber and 10~70 parts reinforcing agent mix, 120 DEG C~
140 DEG C of vacuum kneading 3h~6h form well mixed mixing material；The mixing material is thin logical through three-roller, until without visible
Grain, obtains the base rubber of reinforcement；
3）By the base rubber of reinforcement, crosslinking agent, catalyst and polymerization inhibitor by 100 parts of mass fraction, 6~20 parts, 0.1~0.2
Part is well mixed with 0.02~0.2 part and obtains add-on type liquid fluorosioloxane rubber；
Crosslinking agent can improve the avtive spot with base rubber reaction, increase the molecular weight of base rubber, so as to improve liquid fluorine silicon
The performance of rubber；Catalyst is the initiator for triggering add-on type curing reaction to occur；The effect of polymerization inhibitor is to suppress catalyst
Reactivity, so as to extend operable time.
4）Curing molding：Add-on type liquid fluorosioloxane rubber is molded slice, molding temperature 110 DEG C~130 on vulcanizer
DEG C, time 3min~8min, obtain the add-on type fluorosioloxane rubber of solid-state sheet.
The essence of the crosslinking curing of this method is silicon hydrogenation, i.e., under the catalytic action of catalyst, organic hydride two
Alkene polysiloxanes and vinyl fluoride silicone oil（Base rubber）Between cross-linking and curing reaction, reaction principle is as follows：
Si—H + CH2=CH2—R → Si—CH2CH2—R
Wherein, step 1）Described in D3The purity of F monomers is more than 99.5%；Described ViD4For technical pure level, ViD4It is
The vulcanizing group of base rubber is introduced, it act as add-on type curing reaction and carries enough reactivity sites, can use mass parts
Number substitutes for the dimethyl silicone polymer linear polymer of 0.4 part~0.5 part of ethenyl blocking；MM is also technical pure level, is
The end-capping reagent of base rubber is synthesized, is the chain terminating agent for synthesizing base rubber reaction, can be by the tetramethyl of 0.2 part~0.3 part of mass fraction
Divinyl disiloxane substitutes.Due to the method that the phase uses removed under reduced pressure small molecule before the reaction, ensure initial reaction stage system
In amount of moisture permission scope；And during the course of the reaction, by way of blasting nitrogen, vacuumize guarantee system it is small
Scope of the molecule in permission.
Step 1）Obtained ceridust base fluorosilicon oil is in step 2）In copolymerizable vinyl groups fluorosilicon oil can be used to substitute, this is common
Contents of ethylene in polyvinyl fluorosilicon oil is the mol% of 0.02mol%~1mol%, the mol% of trifluoro propyl content 20~50.
Step 2）In reinforcing agent be that specific surface area is more than 100m2/ g white carbon is placed in 140 DEG C~160 DEG C of drying
4h~6h is reacted in case to be made；Described white carbon is fume colloidal silica or precipitated silica, dosage be mass fraction 10 ~
50 parts；Above-mentioned white carbon can be substituted with carbon black, and its dosage is 30~70 parts of mass fraction.Reinforcing agent rises to liquid fluorosilicone rubber
To the effect of uniformly distributed load, the possibility that liquid fluorosilicone rubber is broken is reduced.
Step 3）In, described crosslinking agent is hydrogeneous fluorosilicon oil or containing hydrogen silicone oil；The hydrogen content of described hydrogeneous fluorosilicon oil
For 0.3%~0.75%, it is to hold that hydrogeneous or side is hydrogeneous, and dosage is 6 ~ 18 parts of mass fraction that its institute is hydrogeneous；Described containing hydrogen silicone oil
Hydrogen content is 0.35%~0.9%, and dosage is 8~20 parts of mass fraction.Step 3）In used catalyst be chloroplatinic acid isopropyl
Alcoholic solution or alkali glue；Polymerization inhibitor in step 3) is alkynol or ViD4；The dosage of described alkynol be 0.02 part of mass fraction ~
0.06 part；Described ViD4Dosage be 0.1~0.2 part of mass fraction.
Step 1）With 3）The preparation method of middle catalyst alkali glue is：It is 150~160 by mass ratio：2~3 D3F and
TMAH mixes, and in 50 DEG C~70 DEG C removed under reduced pressure low-boiling-point substances, and then controlling reaction temperature is at 60 DEG C~80 DEG C,
Reaction time 60min~80min.
Step 3）The crosslinking curing of add-on type liquid fluorosioloxane rubber can be consolidated using cold curing, intermediate temperature setting or high temperature
Change；The condition of described cold curing is at 20 DEG C~25 DEG C, reacts 24~28h；The condition of described intermediate temperature setting is 60
DEG C~80 DEG C, react 30~60min；The condition of described hot setting is at 110 DEG C~130 DEG C, reacts 3~8min.
Step 4）The liquid fluorosilicone rubber that add-on type solidifies can be processed by the way of extrusion, injection pressure, reach mould
The performance requirement of pressure.Or by the liquid fluorosilicone rubber post vulcanization after molding, to eliminate residual stress.
In step 4）Afterwards, temperature is risen to 150 DEG C~180 DEG C, and reacts 0.5h~1h, can lose catalyst alkali glue
Activity.
Compared with prior art, the present invention has the advantages that：
1st, base rubber, after the more excellent process conditions of control ratio, energy are prepared using the method for anion body ring-opening polymerisation
The product of high conversion is obtained, and using the method for polymerisation in bulk, polymerisation in solution, emulsion polymerization can be avoided, facilitate solution, breast
The recovery of liquid, reduce cumbersome technological process and equipment investment.
2nd, the catalyst synthesized using alkali glue as base rubber, the catalyst are temporary catalyst, only need the phase after the reaction
Temperature is risen to 150 DEG C, so that it may lose the activity of catalyst, reduce the technique and equipment of follow-up Removal of catalyst, reduce cost.
3rd, add-on type solidification be applicable to be molded, extrude, the processing technology such as injection pressure, greatly reduce the percent defective of product,
And the generation of non-trimming phenomenon in process, automated production can be achieved.
4th, fume colloidal silica may be selected in reinforcing agent and precipitated silica active filler, the surface of hard charcoal black track producing particle are stronger
Absorption base rubber strand, the usual white carbon particle surface first line of a couplet is connected to several strands, and the physics for forming interchain is handed over
Connection, and the hard charcoal black track producing particle of binding molecule chain can also play a part of uniformly distributed, so as to reduce liquid fluorosilicone rubber hair
The possibility of raw fracture, improve the mechanical property of liquid fluorosilicone rubber.
5th, polymerization inhibitor can extend the operating time in base rubber, be advantageous to site operation and operation.
6th, it can be required according to the application places of liquid fluorosilicone rubber, add metal oxide（Fe2O3、Fe2O3/SnO2、
SnO2、CeO2）High temperature resistant additive and auxiliary agent（Plasticizer, colouring agent）To reach the requirement of application.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
A kind of preparation method of add-on type liquid fluorosioloxane rubber, comprises the following steps：
1）The synthesis of base rubber：The synthesis of base rubber：By raw material D3F、ViD4With MM by 60~70 parts of mass fraction, 0.4~0.5
Part is mixed in three-necked flask with 0.2~0.3 part, in 50 DEG C~70 DEG C removed under reduced pressure low-boiling-point substances, and adds mass fraction as 0.2
~ 0.4 catalyst, nitrogen is filled with as gas is protected, makes reaction temperature at 60 DEG C~80 DEG C, reaction time 40min~60min,
It is base rubber that ceridust base fluorosilicon oil, which is made, and the base rubber medium vinyl content is 0.02mol%~1mol%, and trifluoro propyl content is
The mol% of 20 mol%~50；Described catalyst is alkali glue；
2）The reinforcement of base rubber：By mass fraction be 100 parts base rubber and 10~70 parts reinforcing agent mix, 120 DEG C~
140 DEG C of vacuum kneading 3h~6h form well mixed mixing material；The mixing material is thin logical through three-roller, until without visible
Grain, obtains the base rubber of reinforcement；
3）By the base rubber of reinforcement, crosslinking agent, catalyst and polymerization inhibitor by 100 parts of mass fraction, 6~20 parts, 0.1~0.2
Part is well mixed with 0.02~0.2 part and obtains add-on type liquid fluorosioloxane rubber；
Crosslinking agent can improve the avtive spot with base rubber reaction, increase the molecular weight of base rubber, so as to improve liquid fluorine silicon
The performance of rubber；Catalyst is the initiator for triggering add-on type curing reaction to occur；The effect of polymerization inhibitor is to suppress catalyst
Reactivity, so as to extend operable time.
4）Curing molding：Add-on type liquid fluorosioloxane rubber is molded slice, molding temperature 110 DEG C~130 on vulcanizer
DEG C, time 3min~8min, obtain the add-on type fluorosioloxane rubber of solid-state sheet.
The essence of the crosslinking curing of this method is silicon hydrogenation, i.e., under the catalytic action of catalyst, organic hydride two
Alkene polysiloxanes and vinyl fluoride silicone oil（Base rubber）Between cross-linking and curing reaction, reaction principle is as follows：
Si—H + CH2=CH2—R → Si—CH2CH2—R
Wherein, step 1）Described in D3The purity of F monomers is more than 99.5%；Described ViD4For technical pure level, ViD4It is
The vulcanizing group of base rubber is introduced, it act as add-on type curing reaction and carries enough reactivity sites, can use mass parts
Number substitutes for the dimethyl silicone polymer linear polymer of 0.4 part~0.5 part of ethenyl blocking；MM is also technical pure level, is
The end-capping reagent of base rubber is synthesized, is the chain terminating agent for synthesizing base rubber reaction, can be by the tetramethyl of 0.2 part~0.3 part of mass fraction
Divinyl disiloxane substitutes.Due to the method that the phase uses removed under reduced pressure small molecule before the reaction, ensure initial reaction stage system
In amount of moisture permission scope；And during the course of the reaction, by way of blasting nitrogen, vacuumize guarantee system it is small
Scope of the molecule in permission.
Step 1）Obtained ceridust base fluorosilicon oil is in step 2）In copolymerizable vinyl groups fluorosilicon oil can be used to substitute, this is common
Contents of ethylene in polyvinyl fluorosilicon oil is the mol% of 0.02mol%~1mol%, the mol% of trifluoro propyl content 20~50.
Step 2）In reinforcing agent be that specific surface area is more than 100m2/ g white carbon is placed in 140 DEG C~160 DEG C of drying
4h~6h is reacted in case to be made；Described white carbon is fume colloidal silica or precipitated silica, dosage be mass fraction 10 ~
50 parts；Above-mentioned white carbon can be substituted with carbon black, and its dosage is 30~70 parts of mass fraction.Reinforcing agent rises to liquid fluorosilicone rubber
To the effect of uniformly distributed load, the possibility that liquid fluorosilicone rubber is broken is reduced.
Step 3）In, described crosslinking agent is hydrogeneous fluorosilicon oil or containing hydrogen silicone oil；The hydrogen content of described hydrogeneous fluorosilicon oil
For 0.3%~0.75%, it is to hold that hydrogeneous or side is hydrogeneous, and dosage is 6 ~ 18 parts of mass fraction that its institute is hydrogeneous；Described containing hydrogen silicone oil
Hydrogen content is 0.35%~0.9%, and dosage is 8~20 parts of mass fraction.Step 3）In used catalyst be chloroplatinic acid isopropyl
Alcoholic solution or alkali glue；Polymerization inhibitor in step 3) is alkynol or ViD4；The dosage of described alkynol be 0.02 part of mass fraction ~
0.06 part；Described ViD4Dosage be 0.1~0.2 part of mass fraction.
Step 1）With 3）The preparation method of middle catalyst alkali glue is：It is 150~160 by mass ratio：2~3 D3F and
TMAH mixes, and in 50 DEG C~70 DEG C removed under reduced pressure low-boiling-point substances, and then controlling reaction temperature is at 60 DEG C~80 DEG C,
Reaction time 60min~80min.
Step 3）The crosslinking curing of add-on type liquid fluorosioloxane rubber can be consolidated using cold curing, intermediate temperature setting or high temperature
Change；The condition of described cold curing is at 20 DEG C~25 DEG C, reacts 24~28h；The condition of described intermediate temperature setting is 60
DEG C~80 DEG C, react 30~60min；The condition of described hot setting is at 110 DEG C~130 DEG C, reacts 3~8min.
Step 4）The liquid fluorosilicone rubber that add-on type solidifies can be processed by the way of extrusion, injection pressure, reach mould
The performance requirement of pressure.Or by the liquid fluorosilicone rubber post vulcanization after molding, to eliminate residual stress.
In step 4）Afterwards, temperature is risen to 150 DEG C~180 DEG C, and reacts 0.5h~1h, can lose catalyst alkali glue
Activity.
Embodiment 1
It is prepared as follows add-on type liquid fluorosioloxane rubber：
1）The synthesis of base rubber：By raw material D3F、ViD4With MM three mouthfuls of burnings are mixed in by mass fraction for 62 parts, 0.4 part and 0.2 part
In bottle, in 65 DEG C of removed under reduced pressure low-boiling-point substances, and the catalyst alkali glue that mass fraction is 0.23 is added, be filled with nitrogen as protection
Gas, reaction temperature is set reaction time 45min, to make monomer D at 65 DEG C3F is converted into line polymer, in linear polymer conversion
Terminate before four stable ring bodies, so as to obtain the higher vinyl fluoride silicone oil of conversion ratio；65 DEG C of reaction temperature, catalyst alkali glue
Active temperature be less than cesium hydroxide（70℃）, higher temperature can make the molecular weight distribution of product wider.
2）The reinforcement of base rubber：By base rubber and reinforcing agent white carbon by 100 parts of mass fraction, 30 parts of mixing, in 130 DEG C of vacuum
Mediate 4h and form well mixed mixing material；Certain vacuum ensures to exclude body as far as possible in kneading process small molecular
System, ensure base rubber can maximum capacity capacity reinforcing agent, while also ensure both can be well mixed；Bao Tong, to base rubber with mending
Both strong agent white carbon mixed systems are ground, after 4 times, without visible particle in mixture.
3）The crosslinking curing of add-on type liquid fluorosioloxane rubber：The base rubber of reinforcement, crosslinking agent, catalyst and polymerization inhibitor are pressed into matter
It is well mixed to measure 100 parts, 14 parts, 0.14 part and 0.06 part of portion rate, reacts 25h at room temperature, obtains add-on type liquid fluorine silicon
Rubber；
Described crosslinking agent is the hydrogeneous fluorosilicon oil that hydrogen content is 0.3%~0.75%, and its hydrogeneous institute is to hold hydrogeneous or side to contain
Hydrogen；Described catalyst is alkali glue；Described polymerization inhibitor is alkynol；
4）Curing molding：Add-on type liquid fluorine silicon rubber is molded slice, 120 DEG C of molding temperature, time on vulcanizer
5min, obtain the add-on type fluorosioloxane rubber of solid-state sheet.Too low temperature will ensure that polymer can vulcanize, it is necessary to extend fluidisation
Time, higher temperature can cause film excessively precured.
5）Temperature is risen to 150 DEG C~180 DEG C, and reacts 0.5h.
Embodiment 2
It is prepared as follows add-on type liquid fluorosioloxane rubber：
1）The synthesis of base rubber：By raw material D3F、ViD4With MM three mouthfuls are mixed in by mass fraction for 69 parts, 0.48 part and 0.28 part
In flask, in 68 DEG C of removed under reduced pressure low-boiling-point substances, the alkali glue that mass fraction is 0.4 is added, nitrogen is filled with as protection gas, makes reaction
Temperature is at 76 DEG C, reaction time 55min；
2）The reinforcement of base rubber：It is true at 140 DEG C by base rubber and reinforcing agent white carbon by 100 parts and 50 parts mixing of mass fraction
Sky mediates 6h and forms well mixed mixing material；The mixing material is thin logical through three-roller, until without visible particle, obtain reinforcement
Base rubber；
3）The crosslinking curing of add-on type liquid fluorosioloxane rubber：The base rubber of reinforcement, crosslinking agent, catalyst and polymerization inhibitor are pressed into matter
It is well mixed to measure 100 parts, 18 parts, 0.20 part and 0.04 part of portion rate, reacts 40min at 70 DEG C, obtains add-on type liquid fluorine
Silicon rubber；
Described crosslinking agent is the hydrogeneous fluorosilicon oil that hydrogen content is 0.3%~0.75%, and its hydrogeneous institute is to hold hydrogeneous or side to contain
Hydrogen；Described catalyst is alkali glue；Described polymerization inhibitor is alkynol；
4）Curing molding：Add-on type liquid fluorine silicon rubber is molded slice, 130 DEG C of molding temperature, time on vulcanizer
8in, obtain the add-on type fluorosioloxane rubber of solid-state sheet.
5）Temperature is risen to 150 DEG C~180 DEG C, and reacts 1h.
Embodiment 3
It is prepared as follows add-on type liquid fluorosioloxane rubber：
1）The synthesis of base rubber：By raw material D3F、ViD4With MM three are mixed in by quality parts ratio for 60 parts, 0.45 part and 0.25 part
In mouth flask, in 50 DEG C of removed under reduced pressure low-boiling-point substances, the alkali glue that mass fraction is 0.2 part is added, nitrogen is filled with as protection gas, makes
Reaction temperature is at 60 DEG C, reaction time 40min；
2）The reinforcement of base rubber：By base rubber and reinforcing agent white carbon by 100 parts and 10 parts mixing of quality parts ratio, at 120 DEG C
Vacuum kneading 3h forms well mixed mixing material；The mixing material is thin logical through three-roller, until without visible particle, obtain reinforcement
Base rubber；
3）The crosslinking curing of add-on type liquid fluorosioloxane rubber：The base rubber of reinforcement, crosslinking agent, catalyst and polymerization inhibitor are pressed into matter
It is well mixed to measure 100 parts, 6 parts, 0.1 part and 0.02 part of portion rate, reacts 6min at 120 DEG C, obtains add-on type liquid fluorine silicon
Rubber；
Described crosslinking agent is the hydrogeneous fluorosilicon oil that hydrogen content is 0.3%~0.75%, and its hydrogeneous institute is to hold hydrogeneous or side to contain
Hydrogen；Described catalyst is alkali glue；Described polymerization inhibitor is alkynol；
4）Curing molding：Add-on type liquid fluorine silicon rubber is molded slice, 110 DEG C of molding temperature, time on vulcanizer
3min, obtain the add-on type fluorosioloxane rubber of solid-state sheet.
5）Temperature is risen to 150 DEG C~180 DEG C, and reacts 40min.
Embodiment 4
It is prepared as follows add-on type liquid fluorosioloxane rubber：
1）The synthesis of base rubber：By raw material D3F、ViD4With MM three are mixed in by quality parts ratio for 62 parts, 0.44 part and 0.3 part
In mouth flask, in 55 DEG C of removed under reduced pressure low-boiling-point substances, the alkali glue that mass fraction is 0.35 part is added, nitrogen is filled with and is used as protection gas,
Make reaction temperature at 70 DEG C, reaction time 50min；
2）The reinforcement of base rubber：By base rubber and carbon black by 100 parts and 65 parts mixing of quality parts ratio, in 120 DEG C of vacuum kneadings
3h forms well mixed mixing material；The mixing material is thin logical through three-roller, until without visible particle, obtain the base rubber of reinforcement；
3）The crosslinking curing of add-on type liquid fluorosioloxane rubber：The base rubber of reinforcement, crosslinking agent, catalyst and polymerization inhibitor are pressed into matter
It is well mixed to measure 100 parts, 20 parts, 0.1 part and 0.2 part of portion rate, reacts 8min at 125 DEG C, obtains add-on type liquid fluorine silicon
Rubber；
Described crosslinking agent is the containing hydrogen silicone oil that hydrogen content is 0.35%~0.9%；Described catalyst is different for chloroplatinic acid
Propanol solution；Described polymerization inhibitor is ViD4；
4）Curing molding：Add-on type liquid fluorine silicon rubber is molded slice, 110 DEG C of molding temperature, time on vulcanizer
3min, obtain the add-on type fluorosioloxane rubber of solid-state sheet.
5）Temperature is risen to 150 DEG C~180 DEG C, and reacts 40min.
Embodiment 5
It is prepared as follows add-on type liquid fluorosioloxane rubber：
1）The reinforcement of base rubber：Copolymerizable vinyl groups fluorosilicon oil and carbon black are mixed for 100 parts and 65 parts by quality parts ratio,
120 DEG C of vacuum kneading 3h form well mixed mixing material；The mixing material is thin logical through three-roller, until without visible particle, obtain
To the base rubber of reinforcement；Contents of ethylene in described copolymerizable vinyl groups fluorosilicon oil is 0.02mol%~1mol%, trifluoro propyl contains
Measure the mol% of 20 mol%~50.
2）The crosslinking curing of add-on type liquid fluorosioloxane rubber：The base rubber of reinforcement, crosslinking agent, catalyst and polymerization inhibitor are pressed into matter
It is well mixed to measure 100 parts, 20 parts, 0.1 part and 0.2 part of portion rate, reacts 7min at 115 DEG C, obtains add-on type liquid fluorine silicon
Rubber；
Described crosslinking agent is the containing hydrogen silicone oil that hydrogen content is 0.35%~0.9%；Described catalyst is different for chloroplatinic acid
Propanol solution；Described polymerization inhibitor is ViD4。
3）Curing molding：Add-on type liquid fluorine silicon rubber is molded slice, 110 DEG C of molding temperature, time on vulcanizer
3min, obtain the add-on type fluorosioloxane rubber of solid-state sheet.
4）Temperature is risen to 150 DEG C~180 DEG C, and reacts 40min.
Embodiment 6
It is prepared as follows add-on type liquid fluorosioloxane rubber：
1）The synthesis of base rubber：By raw material D3F、ViD4With MM three are mixed in by quality parts ratio for 66 parts, 0.47 part and 0.28 part
In mouth flask, in 65 DEG C of removed under reduced pressure low-boiling-point substances, the alkali glue that mass fraction is 0.38 part is added, nitrogen is filled with and is used as protection gas,
Make reaction temperature at 70 DEG C, reaction time 50min；
2）The reinforcement of base rubber：By base rubber and carbon black by 100 parts and 30 parts mixing of quality parts ratio, in 120 DEG C of vacuum kneadings
3h forms well mixed mixing material；The mixing material is thin logical through three-roller, until without visible particle, obtain the base rubber of reinforcement；
3）The crosslinking curing of add-on type liquid fluorosioloxane rubber：The base rubber of reinforcement, crosslinking agent, catalyst and polymerization inhibitor are pressed into matter
It is well mixed to measure 100 parts, 8 parts, 0.16 part and 0.1 part of portion rate, reacts 60min at 75 DEG C, obtains add-on type liquid fluorine silicon
Rubber；
Described crosslinking agent is the containing hydrogen silicone oil that hydrogen content is 0.35%~0.9%；Described catalyst is different for chloroplatinic acid
Propanol solution；Described polymerization inhibitor is ViD4；
4）Curing molding：Add-on type liquid fluorine silicon rubber is molded slice, 120 DEG C of molding temperature, time on vulcanizer
7min, obtain the add-on type fluorosioloxane rubber of solid-state sheet.
5）Temperature is risen to 150 DEG C~180 DEG C, and reacts 40min.
Embodiment 7
It is prepared as follows add-on type liquid fluorosioloxane rubber：
1）The synthesis of base rubber：By raw material D3F、ViD4With MM three mouthfuls are mixed in by quality parts ratio for 70 parts, 0.5 part and 0.3 part
In flask, in 65 DEG C of removed under reduced pressure low-boiling-point substances, the alkali glue that mass fraction is 0.3 part is added, nitrogen is filled with as protection gas, makes anti-
Temperature is answered at 63 DEG C, reaction time 48min；
2）The reinforcement of base rubber：By base rubber and carbon black by 100 parts and 50 parts mixing of quality parts ratio, in 120 DEG C of vacuum kneadings
3h forms well mixed mixing material；The mixing material is thin logical through three-roller, until without visible particle, obtain the base rubber of reinforcement；
3）The crosslinking curing of add-on type liquid fluorosioloxane rubber：The base rubber of reinforcement, crosslinking agent, catalyst and polymerization inhibitor are pressed into matter
It is well mixed to measure 100 parts, 15 parts, 0.15 part and 0.15 part of portion rate, reacts 28h at room temperature, obtains add-on type liquid fluorine silicon
Rubber；
Described crosslinking agent is the containing hydrogen silicone oil that hydrogen content is 0.35%~0.9%；Described catalyst is different for chloroplatinic acid
Propanol solution；Described polymerization inhibitor is ViD4；
4）Curing molding：Add-on type liquid fluorine silicon rubber is molded slice, 120 DEG C of molding temperature, time on vulcanizer
5min, obtain the add-on type fluorosioloxane rubber of solid-state sheet.
5）Temperature is risen to 150 DEG C~180 DEG C, and reacts 50min.
The above embodiment of the present invention is only example to illustrate the invention, and is not the implementation to the present invention
The restriction of mode.For those of ordinary skill in the field, other can also be made not on the basis of the above description
With the change and variation of form.Here all embodiments can not be exhaustive.It is every to belong to technical scheme
Row of the obvious changes or variations amplified out still in protection scope of the present invention.
Claims (7)
1. a kind of preparation method of add-on type liquid fluorosioloxane rubber, it is characterised in that comprise the following steps：
1）The synthesis of base rubber：By raw material D3F、ViD460~70 parts, 0.4~0.5 part and 0.2~0.3 part of mass fraction is pressed with MM
It is mixed in three-necked flask, in 50 DEG C~70 DEG C removed under reduced pressure low-boiling-point substances, and adds the catalyst that mass fraction is 0.2 ~ 0.4,
Nitrogen is filled with as protection gas, makes reaction temperature at 60 DEG C~80 DEG C, reaction time 40min~60min, ceridust base is made
Fluorosilicon oil is base rubber, and the base rubber medium vinyl content is 0.02mol%~1mol%, and trifluoro propyl content is 20 mol%~50
mol%；Described catalyst is alkali glue；The preparation method of described alkali glue is：It is 150~160 by mass ratio：2~3 D3F and
TMAH mixes, and in 50 DEG C~70 DEG C removed under reduced pressure low-boiling-point substances, and then controlling reaction temperature is at 60 DEG C~80 DEG C,
Reaction time 60min~80min, the alkali glue that alkali content is 0.075% is made；
2）The reinforcement of base rubber：Mass fraction is mixed for 100 parts of base rubber and 10~70 parts of reinforcing agent, at 120 DEG C~140 DEG C
Vacuum kneading 3h~6h forms well mixed mixing material；The mixing material is thin logical through three-roller, until without visible particle, obtain
The base rubber of reinforcement；
3）The crosslinking curing of add-on type liquid fluorosioloxane rubber：The base rubber of reinforcement, crosslinking agent, catalyst and polymerization inhibitor are pressed into mass parts
100 parts, 6~20 parts, 0.1~0.2 part and 0.02~0.2 part of number is well mixed to carry out crosslinking curing, obtains add-on type liquid fluorine
Silicon rubber；The crosslinking curing of described add-on type liquid fluorosioloxane rubber is cold curing, intermediate temperature setting or hot setting；Described
The condition of cold curing is at 20 DEG C~25 DEG C, reacts 24~28h；The condition of described intermediate temperature setting be at 60 DEG C~80 DEG C,
React 30~60min；The condition of described hot setting is at 110 DEG C~130 DEG C, reacts 3~8min；
4）Curing molding：Add-on type liquid fluorosioloxane rubber is molded slice on vulcanizer, 110 DEG C~130 DEG C of molding temperature, when
Between 3min~8min, obtain the add-on type fluorosioloxane rubber of solid-state sheet；Temperature is risen to 150 DEG C~180 DEG C, and react 0.5h~
1h, so that catalyst loss of activity.
2. the preparation method of add-on type liquid fluorosioloxane rubber according to claim 1, it is characterised in that the ViD4Replace
For 0.4 part~0.5 part of end-vinyl polysiloxanes of mass fraction；Described MM replaces with 0.2 part~0.3 part of mass fraction
Tetramethyl divinyl disiloxane.
3. the preparation method of add-on type liquid fluorosioloxane rubber according to claim 1, it is characterised in that step 1）It is made
Ceridust base fluorosilicon oil replace with copolymerizable vinyl groups fluorosilicon oil, the contents of ethylene in the copolymerizable vinyl groups fluorosilicon oil is
The mol% of 0.02mol%~1mol%, the mol% of trifluoro propyl content 20~50.
4. the preparation method of add-on type liquid fluorosioloxane rubber according to claim 1, it is characterised in that described reinforcing agent
It is that specific surface area is more than 100m2/ g white carbon is placed in reaction 4h~6h in 140 DEG C~160 DEG C of drying box and is made；It is described
White carbon be fume colloidal silica or precipitated silica, dosage is 10 ~ 50 parts of mass fraction；Above-mentioned white carbon replaces with charcoal
Black, its dosage is 30~70 parts of mass fraction.
5. the preparation method of add-on type liquid fluorosioloxane rubber according to claim 1, it is characterised in that step 3）Described in
Crosslinking agent be hydrogeneous fluorosilicon oil or containing hydrogen silicone oil；The hydrogen content of described hydrogeneous fluorosilicon oil is 0.3%~0.75%, and its institute is hydrogeneous
It is that the hydrogeneous or side in end is hydrogeneous, dosage is 6 ~ 18 parts of mass fraction；The hydrogen content of described containing hydrogen silicone oil is 0.35%~0.9%, is used
Measure as 8~20 parts of mass fraction.
6. the preparation method of add-on type liquid fluorosioloxane rubber according to claim 1, it is characterised in that step 3）In it is used
Catalyst be chloroplatinic acid aqueous isopropanol or alkali glue.
7. the preparation method of add-on type liquid fluorosioloxane rubber according to claim 1, it is characterised in that the resistance in step 3)
Poly- agent is alkynol or ViD4；The dosage of described alkynol is 0.02 part ~ 0.06 part of mass fraction；Described ViD4Dosage be matter
Measure 0.1~0.2 part of number.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510614864.7A CN105199106B (en) | 2015-09-24 | 2015-09-24 | A kind of preparation method of add-on type liquid fluorosioloxane rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510614864.7A CN105199106B (en) | 2015-09-24 | 2015-09-24 | A kind of preparation method of add-on type liquid fluorosioloxane rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105199106A CN105199106A (en) | 2015-12-30 |
| CN105199106B true CN105199106B (en) | 2018-01-26 |
Family
ID=54947087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510614864.7A Expired - Fee Related CN105199106B (en) | 2015-09-24 | 2015-09-24 | A kind of preparation method of add-on type liquid fluorosioloxane rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105199106B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109852073A (en) * | 2018-08-30 | 2019-06-07 | 深圳市冠恒新材料科技有限公司 | Add-on type Fluorosilicone rubber composition and preparation method thereof, fluorine silicone rubber and coating |
| CN109265966B (en) * | 2018-09-17 | 2021-05-07 | 上海玉城高分子材料股份有限公司 | Polyurethane/fluorosilicone rubber thermoplastic elastomer for wearable equipment and preparation method thereof |
| CN109385250B (en) * | 2018-10-13 | 2021-02-26 | 东莞市佳迪新材料有限公司 | Preparation and application of tackifier for addition type organic silicon heat-conducting pouring sealant |
| CN110776748A (en) * | 2019-09-18 | 2020-02-11 | 宁波泰意德过滤技术有限公司 | Addition type fluorosilicone rubber and preparation method thereof |
| CN111073306A (en) * | 2019-12-31 | 2020-04-28 | 广东中蓝硅氟新材料有限公司 | Addition type solid conductive fluorosilicone rubber and preparation method thereof |
| CN111073305A (en) * | 2019-12-31 | 2020-04-28 | 广东中蓝硅氟新材料有限公司 | Addition type heat-conducting solid fluorosilicone rubber as well as preparation method and application thereof |
| CN111154454B (en) * | 2020-01-07 | 2022-03-15 | 芜湖福赛尔航空材料股份有限公司 | Oil-resistant silicone sealant |
| CN111234232A (en) * | 2020-03-24 | 2020-06-05 | 抚州市阿璐达新材料有限公司 | Preparation method of fluorosilicone rubber for turbocharger tube |
| CN115181270A (en) * | 2020-06-16 | 2022-10-14 | 湖北兴瑞硅材料有限公司 | Ternary polymerization fluorosilicone rubber and preparation method thereof |
| CN113025059B (en) * | 2021-03-09 | 2022-07-15 | 新元化学(山东)股份有限公司 | High-tear-strength addition type liquid fluorosilicone rubber and preparation method thereof |
| CN113088087A (en) * | 2021-05-19 | 2021-07-09 | 无锡市逸晟硅材料有限公司 | Food-grade antibacterial addition type liquid silicone rubber |
| CN114456605B (en) * | 2022-02-28 | 2023-05-12 | 新元化学(山东)股份有限公司 | Engine oil low-pressure-resistant addition type liquid fluorosilicone rubber and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044665A (en) * | 1989-01-31 | 1990-08-15 | 上海市有机氟材料研究所 | High-strength tear-resistant trifluoropropyl siloxane auxiliary agent (C glue) and preparation thereof |
| CN1702098A (en) * | 2005-06-13 | 2005-11-30 | 上海三爱富新材料股份有限公司 | Fluorine-silicon compounded rubber stock and method for making same |
| CN103013123A (en) * | 2012-12-31 | 2013-04-03 | 成都拓利化工实业有限公司 | Two-component silica gel and preparation method thereof |
| CN103030976A (en) * | 2012-12-27 | 2013-04-10 | 成都拓利化工实业有限公司 | Single-component heat-curing liquid silicone rubber and preparation method thereof |
-
2015
- 2015-09-24 CN CN201510614864.7A patent/CN105199106B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044665A (en) * | 1989-01-31 | 1990-08-15 | 上海市有机氟材料研究所 | High-strength tear-resistant trifluoropropyl siloxane auxiliary agent (C glue) and preparation thereof |
| CN1702098A (en) * | 2005-06-13 | 2005-11-30 | 上海三爱富新材料股份有限公司 | Fluorine-silicon compounded rubber stock and method for making same |
| CN103030976A (en) * | 2012-12-27 | 2013-04-10 | 成都拓利化工实业有限公司 | Single-component heat-curing liquid silicone rubber and preparation method thereof |
| CN103013123A (en) * | 2012-12-31 | 2013-04-03 | 成都拓利化工实业有限公司 | Two-component silica gel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 硅氢加成氟硅橡胶的制备;陈秀杰 杨冲;《城市建设理论研究（电子版）》;20140831;第4卷(第23期);说明书第1页，表3、表6 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105199106A (en) | 2015-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105199106B (en) | A kind of preparation method of add-on type liquid fluorosioloxane rubber | |
| US4029629A (en) | Solvent resistant room temperature vulcanizable silicone rubber composition | |
| CN100482761C (en) | Single-component room-temperature fast sulfidization dealcoholization type sealing rubber with silicone structure and preparing method thereof | |
| CN110845980A (en) | COB packaging adhesive and preparation method thereof | |
| CN109851759B (en) | Organic silicon modified epoxy resin, preparation method thereof and organic silicon modified epoxy resin adhesive | |
| CN103214675B (en) | Poly(methylsilane-carbosilane) and preparation method thereof | |
| CN105670555A (en) | High heat conductivity organosilicon potting compound | |
| CN104327272B (en) | Preparation method of trapezoid polysilsesquioxane-containing block optical transparent condensed-type organic silicone resin | |
| CN103013123A (en) | Two-component silica gel and preparation method thereof | |
| CN110294938A (en) | A kind of mold glue of high-tear strength and preparation method thereof | |
| CN103044920A (en) | One-component room temperature vulcanized and methyl alcohol-removed silicon rubber of starting-resistant engine oil and preparation method of rubber | |
| CN106750092A (en) | A kind of compound polyurethane material for laying plastic cement race track and preparation method thereof | |
| CN108251033A (en) | A kind of automobile thin film capacitor embedding special epoxy resin glue and preparation method thereof | |
| CN115404025B (en) | Polyhydroxy cyclic polymer/polysiloxane modified epoxy resin, and preparation method and application thereof | |
| CN106753217B (en) | A kind of preparation method of novel heat cure liquid silastic | |
| CN106833503A (en) | A kind of single-component ketoxime removing type room temperature vulcanized silicone sealant of low modulus and preparation method thereof | |
| CN109852334A (en) | A kind of anti-settling bi-component organic silicon potting adhesive and preparation method thereof | |
| CN105385408B (en) | Antifatigue, uvioresistant single-component dealcoholization-type silicone structure sealant and preparation method | |
| CN110484197A (en) | A kind of preparation method of room curing and high temperature resistant silicone adhesives | |
| CN104231290B (en) | A kind of adhesive bonding method of fluorosioloxane rubber and silicon rubber | |
| CN116948587B (en) | Preparation and application of bi-component silane modified polyether sealant | |
| CN109777343A (en) | Cured bi-component organic silicon potting adhesive and preparation method thereof is synchronized inside and outside one kind | |
| CN103450444B (en) | A kind of fluorine silicon Modified Waterborne Polyurethane emulsion and preparation method thereof | |
| CN104231638B (en) | A kind of tackifier of fluorosioloxane rubber and silicon rubber and preparation method and application | |
| CN109852071A (en) | Fluorosilicone rubber composition, preparation method and the sealant and coating prepared by the composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 643000 Sichuan Province, Zigong City Hing Road Xueyuan street 180# Applicant after: SICHUAN University OF SCIENCE & ENGINEERING Applicant after: CHENGDU TALY TECHNOLOGY Co.,Ltd. Address before: 643000 Sichuan Province, Zigong City Hing Road Xueyuan street 180# Applicant before: Sichuan University of Science & Engineering Applicant before: CHENGDU TALY CHEMICAL INDUSTRIAL CO.,LTD. |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180126 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |